Non-aqueous dyeing of polyamides with water-soluble amoric dyestuffs dissolved in halogenated hydro-carbons

ABSTRACT

A process for the non-aqueous dyeing or printing of nitrogencontaining fibre material, especially fibre material made from natural or synthetic polyamide, with certain water-soluble anionic anthraquinone dyestuffs from non-polar, aprotic organic solvents is disclosed. By said process even, strongly-coloured dyeings having good fastness properties are obtained; said process is moreover advantageous in that it can be carried out without the use of solubilising agents and without fire hazard in a uniform solvent which can be easily regenerated.

United States Patent [191,

Zenh'ziusern et al.

1 Dec. 18, 1 973 [75] Inventors: Anton Zenhausern, Reinach; JakobBiihler, Muttenz, both of Switzerland [73] Assignee: Ciba-Geigy AG,Basel, Switzerland [22] Filed: Dec. 15, 1970 [21] Appl. No.: 98,455

[30] Foreign Application Priority Data Dec. 16, I969 Switzerland18708/69 [52] -U.S. Cl. 8/39, 8/21 B, 8/82,

[51] Int. Cl. C09b 1/26, D06p 1/20 [58] Field of Search 8/21, 39;260/378 [56] References Cited UNITED STATES PATENTS 3,510,243 5/1970Seuret et al 8/39 3,320,021 5/1967 Guenthard 8/39 3,491,126 1/1970Schwander et al. 260/374 3,434,792 3/1969 Lewis .1 8/39 FOREIGN PATENTSOR APPLICATIONS 1,581,325 9/1969 France OTHER PUBLICATIONS MilicevicText. Chem. & Col., Vol. 2, 5), 1970, p. 17-20, 25-28.

Primary Examiner-George F. Lesmes Assistant Examiner-Patricia C. IvesAttorney-Wenderoth, Lind & Ponack ABSTRACT A process for the non-aqueousdyeing or printing of nitrogen-containing fibre material, especiallyfibre material made from natural or synthetic polyamide, with certainwater-soluble anionic anthraquinone dyestuffs from non-polar, aproticorganic solvents is disclosed. By said process even, strongly-coloureddyeings having good fastness properties are obtained; said process ismoreover advantageous in that it can be carried out without the use ofsolubilising agents and without fire hazard in a uniform solvent whichcan be easily regenerated.

8 Claims, No Drawings NON-AQUEOUS DYEING OF POLYAMIDES WITHWATER-SOLUBLE AMORIC DYESTUFFS DllSSOLVED IN HALOGENATED HYDRO-CARBONSThe present invention relates to a process for the dyeing ornitrogen-containing fibre material, particularly natural and syntheticpolyamide fibres, such as wool and nylon, with water-soluble anionicdyestuffs in organic solvents as well as the fibre material dyed by thisprocess.

It is known that natural and synthetic polyamide fibres can be dyed withanionic water soluble dyestuffs in an aqueous solution. Lately, however,attempts have been made to replace the aqueous medium for the dyeingprocess by organic solvents. This would be very desirable, especially inview of the problems connected with the waste waters. Moreover, whenusing organic solvents, the fibre material can be pre-treated, dyed andafter-treated in the same bath. While organic solvents have been readilyadopted by the industry for the dry cleaning, their use in textiledyeing still meets with a series of problems. In particular, thesolubility of usual water-soluble dyestuffs in organic media representsa problem which has not been solved satisfactorily up to now.

Attempts have been made to transform the usual organic dyestuffs,employed in the form of water-soluble sodium sulphonates, with organicamines into waterinsoluble salts which are soluble in organic media;this additional processing step, however, results in a substantialincrease in cost of the dyestuffs. Furthermore, also strongly polarorganic solvents, such as methanol or ethanol, alone or as solubilizingagents, in admixture with non-polar organic solvents have already beenused. Finally, attempts have been made to effect dyeing with solventemulsions instead of homogeneous mixtures.

While the use of polar organic solvents leads to technical difficulties,especially due to the fire hazard connected therewith, the use ofsolvent emulsions is undesirable from a tinctorial viewpoint.

It has been found that the usual application form of certainwater-soluble anionic dyestuffs which correspond to the general Formulael and ll l J (H) can be used directly for the dyeing of nitrogencontaining fibre material in non-polar aprotic organic solvents.

In said Formulae l and II:

R represents an alkyl group having from I to 12 carbon atoms or acyclohexyl radical unsubstituted or substituted by lower alkyl groups,

R represents hydrogen or a lower alkyl group,

R represents a lower alkylene radical,

W represents hydrogen or the methyl group,

X represents hydrogen, an alkyl group having from I to 12 carbon atoms,the cyclohexyl radical or an optionally substituted aryloxy radical,

Y represents hydrogen, a lower alkyl group, the trifluoromethyl group, alower alkoxy group or a halogen atom,

Z represents hydrogen, a lower alkyl group or a lower alkoxy group, and

M represents an alkali metal cation, ammonium or half the equivalent ofthe charge of an alkaline earth metal cation. The expression lower inconnection with alkyl or alkoxy or an aliphatic halogenated hydrocarbonmeans that the respective radical or the respective compound have from Ito 4 carbon atoms; such radicals are, e.g., methyl, ethyl, isopropyl,n.butyl, sec.butyl, isobutyl or tert.butyl radicals.

R in the meaning of an alkyl group having from I to 12 carbon atomsrepresents, for example, methyl, isopropyl, 1,2-dimethylpropyl, butyl,sec.butyl, 1,3- dimethylbutyl, isohexyl, 2-ethylhexyl, octyl, decyl anddodecyl. If R represents a cyclohexyl radical substituted by lower alkylgroups then it represents, e.g., the 4-methylcyclohexyl radical,3,5,5-trimethylcyclohexyl radical or 4-tert.butylcyclohexyl radical.

R in the meaning of a lower alkylene radical represents, for example, amethylene, dimethylene, propylene or trimethylene radical.

The meaning of X as an alkyl group having from I to 12 carbon atomscorresponds to that given above for R. X, in the meaning of anoptionally substituted aryloxy radical preferably represents a phenoxyradical, unsubstituted or substituted by halogen atoms, such as chlorineor bromine, or alkyl or alkoxy groups having from 1 to 5 carbon atoms.

If Y represents a halogen atom, fluorine, chlorine or bromine are meant,for instance.

Examples of M in the meaning of an alkali metal cation are the lithium,sodium or potassium cation; examples of M in the meaning of an alkalineearth metal cation are the magnesium, strontium or barium cation.

Preferably, R represents a branched lower alkyl group such as the sec.butyl group, more particularly, however, the isopropyl group, or thecyclohexyl radical.

W and Z, preferably each represent hydrogen, while X preferablyrepresents hydrogen or a methylphenoxy radical.

Y preferably represents hydrogen, particularly, however, a lower alkylgroup or a halogen atom, especially the methyl group, the ethyl group orchlorine.

R preferably represents a methyl or an isobutyl group, while R ispreferably the dimethylene radical. M preferably represents an alkalimetal cation and more particularly the sodium cation.

Dyestuffs of the general Formula I, wherein R represents a lower alkylgroup or an optionally methylsubstituted cyclohexyl radical, W and Zeach represent hydrogen, X represents hydrogen or a methylphenoxyradical, Y represents a lower alkyl group or a halogen atom, and Mrepresents an alkali metal cation, more particularly those wherein R andY each represent a lower alkyl group, W, X and Z each represent hydrogenand M represents the sodium cation, have proved particularly suitable.

Dyestuffs of the general Formula II, wherein R represents a lower alkylgroup, especially isopropyl, R represents a lower alkyl group,especially isobutyl, R represents the dimethylene radical, Y and Z eachrepresent hydrogen, and M represents an alkali metal cation,particularly the sodium cation, are also preferred.

in the following, examples of dyestuffs of Formula I, usable accordingto the invention, are listed, the position of the sulphonic acid groupon the phenyl radical being indicated by Q when said position cannot bedetermined:

l-methylamino-4-( 2-sodium-sulpho-4-tert.butyl)-phenylamino-anthraquinone,

l-isopropylamino-4-( 2-sodium-sulpho-4-octyl)-phenylaminc-anthraquinone,

l-isopropylamino-4-( 2-sodium-sulpho-4-dodecylphenylamino-anthraquinone,

l-isopropylamino-4-(2-sodium-sulpho-4-cyclohexyl)-phenylamino-anthraquinone,l-isopropylamino-4-(Q-sodium-sulpho-3-trifluoromethyl)-phenylamino-anthraquinone,lisopropylamino-4-(Q-sodium-sulpho-2,S-dibutoxy)-phenylamino-anthraquinone,l-isopropylamino-4-(Q-sodium-sulpho-2-methyl-6-ethyl)-phenylamino-anthraquinone,l-isopropylamino-4-(Q-sodium-sulpho-2,6-diethoxy)-phenylamino-anthraquinone,l-isopropylamino-4-(2-sodium-sulpho-3,4,5-trimethyl)-phenylamino-anthraquinone,1-isopropylamino-4-(Q-sodium-sulpho-3 ,S-di-tert-.butyl)-phenylamino-anthraquinone, l-isopropylamino-4-( 2,3 ,5,6-tetramethyl-4-sodiumsulpho)-phenylamino-anthraquinone,l-isopropylamino-4-( Q-sodium-sulpho-4-butoxy phenylamino-anthraquinone,

l-sec.butylamino-4-( 2-magnesium-sulpho-4-methyl)-phenylamino-anthraquinone,1-sec.butylamino-4-(Q-sodium-sulpho-4-bromo)- phenylaminc-anthraquinone,l-sec.butylamino-4-(Q-sodium-sulpho-3-methoxy-4-methyl)-phenylamino-anthraquinone,

l-( l ,Z-dimethyl )-propylamino-4-( Z-sodium-sulpho-4-methyl)-phenylamino-anthraquinone,

l-( 1,3-dimethyl )-butylamino-4-( 2-sodium-sulpho-4-methyl)-phenylamino-anthraquinone,

l-( 2-ethyl )-hexylamino-4-( 2-sodium-sulpho-4-methyl)-phenylamino-anthraquinone,

l-octylam ino-4-( 2-potassium-sulpho-4-methyl)-phenylamino-anthraquinone,

l-dodecylamino-4-( 2-ammonium-sulpho-4-methyl)-phenylamino-anthraquinone, l-cyclohexylamino-4-( 2-sodium-sulpho-4-butylphenylamino-anthraquinone, l-cyclohexylamino-4-(2-sodium-sulpho-4-isopropyl)-phenylamino-anthraquinone,

l-(4-tert.butyl)-cyclohexylamino-4-(Q-sodiumsulpho-3-methoxy-4-methyl)-phenylaminoanthraquinone,

l-(3,5,S-trimethyl)-cyclohexylamino-4-(2-lithiumsulpho-4-methyl)-phenylamino-anthraquinone.

Dyestuffs of Formula I, particularly suitable for the process accordingto the invention, are:

l-isopropylamino-4-(2-sodium-sulpho-4-ethyl)- phenylamino-anthraquinone,

l-isopropylamino-4-(Q-sodium-sulpho-4-chloro)-phenylaminc-anthraquinone,

l-sec.butylamino-4-(2-sodium-sulpho-4-methyl)-phenylamino-anthraquinone,

l-cyclohexylamino-4-(2-sodium-sulpho-4-methyl)-phenylamino-anthraquinone,

l-( 3 '-dimethyl-5 '-methylcyclohexylamino)-4-[Q-sodium-sulpho-4-(4"-methylphenoxy)]- phenylamino-anthraquinone,

1-(3'-dimethyl-5'-methylcyclohexylamino)-4-(Q-sodium-sulpho-4-chloro-2-phenoxy)-phenylaminoanthraquinone,

l-(3'-dimethyl-5-methylcyclohexylamino)-4-[Q-sodium-sulpho-2-(2"-methylphenoxy)]- phenylamino-anthraquinone,

l-( 3 -dimethyl-5 '-methylcyclohexylamino)-4-[Q-sodium-sulpho-2-(4"-n.amylphenoxy)]- phenylamino-anthraquinone, moreparticularly, however,

l-isopropylamino-4-(2-sodium-sulpho-4-methyl)-phenylamino-anthraquinone.

Examples of dyestuffs of Formula I], usable according to the invention,in which the position of the sulphonic acid group on the phenyl radicalcannot be determined and is equally designated by Q, are:

l-isopropylamino-4-[ l '-isobutyl-3 '-(Q''-lithiumsulpho)-phenyl]-propylamino-anthraquinone,

l-isopropylamino-4-[ l '-isobutyl-3 Q'-potassiumsulpho)-phenyl]-propylamino-anthraquinone,

l-isopropylamino-4-[l '-methyl-3-(Q"-sodiumsulpho-2"-dimethyl)-phenyl]-propylaminoanthraquinone,

l-isopropylamino-4-[l '-isobutyl-3 '-(Q' '-sodiumsulpho-4 '-methyl)-phenyl ]-propylaminoanthraquinone,

1-isopropylamino-4-[ 1 '-isobutyl-3 '-(Q'-sodiumsulpho-4"-methoxy)-phenyl]-propylaminoanthraquinone,

1-isopropylamino-4-[ l '-isobutyl-3 '-(Q '-sodiumsulpho-2 '5 '-dimethoxy)-phenyl -propylaminoanthraquinone,

l-isopropylamino-4-[ 1 '-isobutyl-3 -(Q'-sodiumsulpho-4"-chloro)-phenyll-propylaminoanthraquinone,

l-isopropylamino-4-[ 1 '-isobutyl-3 '-(Q' -sodium- @5562"-bromo)-phenyl]-propylarnino anthraquinone,

l-sec.butylamino-4-[ l '-isobutyl-3 '-(Q' '-sodiumsulpho)-phenyl]-propylamino-anthraquinone,

l-sec.butylamino-4-[ l '-isob ut yl-3-(Q"-sodiumsulpho-4''-isopropyl-phenyl]-propylaminoanthraquinone,

lsec.butylamino-4-[ l -isobutyl-3'-(Q"-sodiumsulpho-4 '-butoxy )-phenyl-propylaminoanthraquinone,

l-(l,Z-dimethyl)-propylamino-4-[1 '-methyl-2'-(Q"-sodium-sulpho)-phenyl]-ethylaminoanthraquinone,

1-( l,Z-dimethyl)-propylamino-4-[ l -methyl-2'-(Q"-sodium-sulpho-3",5"-dibutoxy)-phenyl]- ethylamino-anthraquinone,

l-dodecylamino-4-[ 2-methy1-'3'-(Q"-sodiumsulpho)-phenyl]-propylamino-anthraquinone,

l-(1,Z-dimethyl)-propylamino-4-[l'-methyl-2-(Q"- sodium-sulpho-Z ",5'-dibutyl )-phenyl ethylamino-anthraquinone,

l-butylamino-4-[ l -methyl-2-(Q"-sodium-sulpho)-phenyl]-ethylamino-anthraquinone,

l-( l,3-dimethy1)-buty1amino-4-[l',2'-dimethyl-3'-(Q"-sodium-sulpho)-phenyll-propylaminoanthraquinone,

l-octylamino-4-[1'-isobutyl-3'-(Q"-potassiumsulpho)-phenyl]-propylamino-anthraquinone,

1-dodecylamino-4-[1 '-isobutyl-3-(Q"-ammoniumsulpho)-phenyll-propylamino-anthraquinone,

l-cyclohexylamino-4-[ l '-isobutyl-3 -(Q"-magnesium-sulpho)-phenyl]-propylaminoanthraquinone,

l-cyclohexylamino-4-[ l-isobutyl-3 '-(Q"-potassiumsulpho-4-butyl)-phenyll-propylaminoanthraquinone,

1*( 3,5 ,S-trimethyl)-cyclohexylamino-4-[ l -methyl-2'-(Q"-potassium-sulpho)-phenyl]-ethylaminoanthraquinone,

l-(3,5,S-trimethyl)-cyclohexylamino-4-[ 1 '-methyl-2'-(Q"-sodium-sulpho-3"-trifluoromethyl)-phenyl]-ethylamino-anthraquinone. I

Of the dyestuffs corresponding to Formula II 1- isopropylamino-4-[ l'-isobutyl-3-(Q"-sodiumsulpho)-phenyl]-propylamino-anthraquinone isparticularly suitable for the process according to the invention.

The anionic dyestuffs, usable according to the invention, can beprepared by methods known per se. Dyestuffs of Formula I are obtained,e.g., by reacting a 1- alkylamino-4-bromo-anthraquinone with thecorresponding phenylamine free from sulphonic acid groups, in solutionor in the melt of excess phenylamine, in the presence of copper or acopper compound, such as copper(l)chloride, and an acid-binding agent,such as sodium acetate, and subsequently sulphonating the resulting1-alkylamino-4phenylamino-anthraquinone compound.

Dyestuffs of Formula II can be prepared in an analogous manner byreacting a l-alkylamino-4-bromoanthraquinone with the correspondingaralkylamine and subsequent sulphonating.

Examples of non-polar aprotic solvents suitable for the processaccording to the invention are liquid hydrocarbons boiling above 30 C,i.e., aromatic hydrocarbons such as xylene or chlorobenzene, principallydichlorobenzene, trichlorobenzene or tetrahydronaphthalene, aliphatichydrocarbons such as hexane, heptane, octane or decane, aliphaticperfluorohydrocarbons such as perfluorohexane or perfiuoroheptane, andcycloaliphatic hydrocarbons such as cyclohexane, particularlycyclohexene. However, in view of their generally better regenerationproperty and non-combustibility, preferably lower aliphatic halogenatedhydrocarbons are used, especially lower aliphatic chlorinatedhydrocarbons, e.g., dichloromethane, chloroform, carbon tetrachloride,trichloroethylene, tribromoethylene, tetrachloroethylene(perchloroethylene), trichloroethane, tetrachloroethane, l,l,2-trichloro-2,2, 1 -trifluo'roethane, 1,1 ,l ,2-tetrachloro-2,2-difluoroethane, pentachlorofluoroethane or l-chloro-3-fluoropropane.Also mixtures of such solvents can be used. Moreover, the solvents cancontain stabilizing agents which is the case quite often with technicalproducts such as the 1,1 ,l-trichloroethane known under the trade nameChlorothene NU (Dow Chemical Co., Midland, Michigan, USA).

Trichloroethylene, more particularly, however, tetrachloroethylene, areespecially suitable as non-polar aprotic solvent.

Examples of nitrogen-containing fibre material are proteinic fibres suchas wool and silk, fibres made from polyurethanes, particularly howeverfibre material made from synthetic polyamide. In the case of wool,dyeing is preferably carried out in the presence of from 1 to 5 percentby weight of water, calculated on the weight of the dye liquor, and,optionally in the presence of a small amount of an emulsifying agent.

As fibre material made from synthetic polyamide which can be dyed by theprocess according to the invention, the following can be mentioned asexamples: condensation products from hexamethylene diamine and adipicacid (Polyamide 6.6) or sebacic acid (Po1yamide 6.10) or mixedcondensation products, e.g. those from hexamethylene diamine, adipicacid and e-caprolactam (Polyamide 6.6/6), also polymerisation productsfrom e-caprolactam, known under the trade names Nylon 6, Perlon, Grilonor Enkalon, or those from w-aminoundecanoic acid (Polyamide l l andRilsan, respectively).

These fibres can be used in any desired form, thus, e.g., in the form ofloose material, rovings, yarns or knitted goods such as knitted fabrics,woven fabrics and bonded fabrics as well as textile floor coverings suchas woven, tufted or matted carpets.

Also blends of such fibres, particularly wool/polyamide blends can beemployed.

Advantageously, the dyeing of the fibre material is carried out by theusual dis-continuous or continuous processes, e.g. according to theexhaustion process, or

by impregnating the fibre material such as by nippadding, spraying orprinting, preferably, however, by padding. 7

In the exhaustion process the fibre material is dyed in a stationarybath in loose form or attached to mechanical devices. Depending on thetype of the goods to be dyed, especially jiggers, winch machines, cheesewinders or similar dyeing apparatuses are employed for this purpose. Thedyestuff is dissolved in the organic solvent, whereupon the fibrematerial is introduced into the dye liquor, at a liquor ratio of from1:5 to 1:100. After having heated the dye bath to the desiredtemperature, which depends on the solvent chosen and the type of fibresand which generally is comprised between 40 and C, dyeing is performedfor about 5 to 45 minutes at this temperature. Thereafter the dyeing,conveniently after rinsing with the non-polar aprotic solvent, is dried.The dyeing can also be carried out at a temperature above the boilingtemperature of the solvent in a closed system.

The dyestuffs can also be applied to the fibre material according to theso-called space-dyeing method (random dyeing) by injecting the dyeliquor into packages by means of hollow needles, and other knownprocesses.

In the case of the pad-dyeing method the dyestuffs are preferablydissolved in the non-polar aprotic solvent. Then the fibre material isguided through the dye solution, advantageously at' room temperature,and then squeezed out to the desired content of impregnating liquor ofabout 60 to 100 percent by weight (referred to the dry weight of thegoods). The major portion of the solvent remaining in the fibre materialis then usually removed under mild conditions, for instance in a streamof warm air at temperatures up to 100 C, depending on the solvent.Fixing of the dyestuff on the thus dried fibre material can be effectedby steaming, e.g. with aqueous steam or with solvent steam, or,preferably by a dry heat treatment at temperatures below the softeningpoint of the fibre material. These two types of heat treatment can alsobe combined. For the dry heat treatment contact heat, a dry stream ofhot air, infra-red irradiation or the action of high frequencyalternating currents are suitable. The dry heat treatment by means ofcontact heat, however, has proved to be particularly useful. For thispurpose, the pre-dried goods are advantageously guided over heatedrotating cylinders for 10 to 30 seconds and at temperature of from 160to 230 C, depending on the type of fibre. Another embodiment of thecontact-heat fixing, which is particularly suitable for laboratory uses,consists in fixing the dyeing in a precision tailors press for thecorresponding times and at the temperatures mentioned above.

Naturally, the dyestuffs can be added to the dye liquors in solid formas well as in the form of concentrated stable solutions.

By the process of this invention level, strongly coloured dyeings areobtained on said fibre material, said dyeings being distinguished bytheir good fastness properties, especially fastness to light, drycleaning, washing, sublimation and rubbing, without any aftertreatment.

Compared with known processes for the dyeing from organic solvents, theprocess of this invention is especially advantageous in that it can becarried out in uniform solvents which do not constitute fire hazard,without requiring any modification of the dyestuffs otherwise usuallyemployed in aqueous dyeing processes. The use of uniform solventsinstead of mixtures of solvents consisting of polar and non-polarsolvents simplifies the regeneration of the solvents. It is verysurprising that the same anionic dyestuffs which can be applied in theusual dyeing processes from aqueous solution, without addition ofsolubilizing agents, are soluble in the non-polar aprotic solvents,usable according to the invention, to such an extent so as to yieldsufiiciently deep dyeings.

The following Examples illustrate the invention. Therein thetemperatures are given in degrees Centigrade.

EXAMPLE 1 5 g of the dyestuff of the Formula are dissolved in 1,000 mlof trichloroethylene A fabric made from Polyamide 6.6 filament is paddedat room temperature with the obtained clear blue dye solution, theimpregnated fabric is squeezed out to a liquor content of about 60percent, calculated on the dry weight of the goods, and dried for 1minute at about 100. The dried dyeing is then fixed for 15 seconds at220 by means of contact heat. Without any after-treatment, a stronglycoloured, even and well developed greenish blue dyeing having excellentfastness to light and wet processing is obtained.

Similar results are achieved, if in the above Example the 1,000 ml oftrichloroethylene are replaced by 1,000 ml of trichloroethane or 1,000ml of dichloromethane.

EXAMPLE 2 If, instead of a fabric made from Polyamide 6.6 filament afabric made from Polyamide 6 is used, and the dyeing is fixed for 15minutes at 190 by means of contact heat, the procedure being otherwiseas described in Example 1, a strongly coloured greenish blue dyeinghaving good fastness properties is also obtained.

EXAMPLE 3 5 g of the dyestuff of the Formula I O IEIH-CHCHz-CH:

| NH-Q-CH;

are dissolved in 1,000 m] of tetrachloroethylene. Fabric made fromPolyamide 6.6 filament is padded at room temperature with the filteredblue solution, the impregnated fabric is squeezed out to a liquorcontent of about percent, calculated on the dry weight of the goods, anddried for about 1 minute at The dried dyeing is then fixed for 15seconds at 220 by means of contact heat.

Without any after-treatment, a strongly coloured, level and welldeveloped greenish blue dyeing having very good fastness to light andwet processing is obtained.

If, instead of the dyestuff mentioned in this Example, 5 g of one of thedyestuffs given in the following'Table l are used, the procedure beingotherwise as described, greenish to reddish blue dyeings on fabric madefrom Polyamide 6.6 filament are obtained in an analogous manner.

employed and instead of the above-described blended fabric a fabric madefrom synthetic polyamide is used, the procedure being otherwise asdescribed, similar re d dish blue dyeings are obtained.

volume of trichloroethane, dichloromethane, trichloroethylene ortetrachloroethylene.

lf, instead of the dyestuff used in this Example, 5 g of one of thedyestuffs given in the following Table ll are TABLE II NHR are dissolvedin 1,000 ml of trichloroethylene. A fabric made from Polyamide 6.6filament is padded at room temperature with the obtained clear blue dyesolution, the impregnated fabric is squeezed out to a liquor content ofabout 70 percent, referred to the dry weight of the fabric, and driedfor about 1 minute at 100. The dried dyeing is then fixed for l5 secondsat 220 by means of contact heat. Without any after-treatment, a stronglycoloured, even and well developed blue dyeing having good fastness tolight and wet processing is obtained. I lf, in the above Example,instead of the dyestuff mentioned 5 g of one of the dyestuffs given inthe following Table III are used, the procedure being otherwise asdescribed, blue dyeings on fabric made from Polyamide 6.6 filament areobtained in an analogous manner.

. TABLE III EXAMPLE 60 0.05 g of the dyestuff of Example 3 are dissolvedin 2.5 g of water, the resulting solution being then admixed with 0.5 gof an emulsifying agent which substantially consists of the salt fromdodecylbenzene sulphonic acid and iso-propoxy-propylamine, and 97 g oftrichloroethylene. Then 5 g of wool flannel are introduced at into thedye bath, the bath is heated in a closed system to 100 within l0 minutesand dyeing is performed for 30 minutes at this temperature. Finally, thedyeing is rinsed and dried as described in Example 59.

A level, greenish blue dyeing is obtained.

EXAMPLE 61 0.05 g of the dyestuff of Example 1 are dissolved in 100 g oftrichloroethylene. At 20 5 g of a fabric made from Polyamide 6.6 staplefibres are introduced into this solution, the bath is heated in a closedsystem to 100 within 15 minutes and dyeing is continued for another 20minutes at this temperature.

The dyeing is rinsed with trichloroethylene and dried in a stream of airat 40. A greenish blue dyeing is obtained.

What we claim is: v

1. In a process for the non-aqueous dyeing of natural or syntheticpolyamide fibre material with solutions of water-soluble anionicdyestuffs in non-polar aprotic organic solvents, the improvement whereinthere is employed a. at least one water-soluble anionic dyestuff of thegeneral Formulae I and II NHR Dyestufi M+ \l/ 2 a 1 X 0 NH L Q4 03 6 5 zExample R W X I Y z' M Shade on No. polyamide 56 CH3 CH3 H 4-Cl H NaBlue.

CH3 g 57 Same as above H 2 O@ H H Na Do.

68 Same as above H H Na Do.

2-0 n.C5Hn

EXAMPLE 59 o NHR 0.05 g of the dyestuff of Examplel are dissolved in v99.5 g of tetrachloroeth'ylene. At 40 5 g of a fabric made fromPolyamide 6.6 staple fibres are introduced into the dye bath, the bathis heated in a closed system to 120 within 10 minutes, and dyeing isperformed'for 30 minutes at this temperature. After rinsing intetrachloroethylene and drying in a stream of air at 40, astronglycoloured, greenish blue dyeing is obtained.

wherein R represents an alkyl group having from 1 to 12 carbon atoms ora cyclohexyl radical unsubstituted or substituted by lower alkyl groups,

R represents hydrogen or a lower alkyl group,

R represents a lower alkylene radical,

W represents hydrogen or a methyl group,

X represents hydrogen, an alkyl group having from 1 to 12 carbon atoms,the cyclohexyl radical or a phenoxy radical unsubstituted or substitutedby halogen atoms, alkyl or alkoxy groups having from 1 to carbon atoms,

Y represents hydrogen, a lower alkyl group, the trifluoromethyl group, alower alkoxy group or a halogen atom,

Z represents hydrogen, a lower alkyl group or a lower alkoxy group, and

M* represents an alkali metal cation, ammonium or half the equivalent ofthe charge of an alkaline earth metal cation, dissolved in b. anunsubstituted or halogenated aromatic, aliphatic or cycloaliphaticliquid hydrocarbon having a boiling point above 30C, or mixtures of suchnon-polar aprotic organic solvent.

2. A process as defined in claim 1 wherein the dyestuff is awater-soluble anionic dyestuff of Formula I, wherein R represents alower alkyl group or a cyclohexyl radical unsubstituted or substitutedby methyl, W

. l6 and Z each represent hydrogen, X represents hydrogen or amethylphenoxy radical, Y represents a lower alkyl group or a halogenatom, and M represents an alkali metal cation.

3. A process as defined in claim 1 wherein the dyestuff is awater-soluble anionic dyestuff of Formula I wherein R and Y eachrepresent a lower alkyl group, W, X and 2 each represent hydrogen and Mrepresents the sodium cation.

4. A process as defined in claim 1 wherein the dyestuff is awater-soluble anionic dyestufi of Formula ll wherein R and R eachrepresent a lower alkyl group, R represents the dimethylene radical, Yand Z each represent hydrogen and M represents an alkali metal cation.

5. A process as defined in claim 1, wherein said hydrocarbon solventdefined under (b) is selected from xylene, monochlorobenzene,dichlorobenzene, trichlorobenzene, tetrahydronaphthalene, hexane,heptane, octane, decane, perfluorohexane, perfluoroheptane, cyclohexane,cyclohexene, dichloromethane, chloroform, carbon tetrachloride,trichloroethylene, tribromoethylene, tetrachloroethylene,trichloroethane, tetrachloroethane, l,l ,2-trichloro-2,2, ltrifluoroethane, 1,1 ,l ,2-tetrachloro-2,2- difluoroethane,pentachlorofluoroethane, l-chloro-3- fluoropropane, and mixturesthereof.

6. A process as defined in claim 1, wherein said hydrocarbon solventdefined under (b) is a lower aliphatic chlorinated hydrocarbon.

7. A process as defined in claim 6, wherein said lower aliphaticchlorinated hydrocarbon is tetrachloroethylene.

8. A process as defined in claim 1 wherein the fiber material issynthetic polyamide fibre material.

2. A process as defined in claim 1 wherein the dyestuff is awater-soluble anionic dyestuff of Formula I, wherein R represents alower alkyl group or a cyclohexyl radical unsubstituted or substitutedby methyl, W and Z each represent hydrogen, X represents hydrogen or amethylphenoxy radical, Y represents a lower alkyl group or a halogenatom, and M represents an alkali metal cation.
 3. A process as definedin claim 1 wherein the dyestuff is a water-soluble anionic dyestuff ofFormula I wherein R and Y each represent a lower alkyl group, W, X and Zeach represent hydrogen and M represents the sodium cation.
 4. A processas defined in claiM 1 wherein the dyestuff is a water-soluble anionicdyestuff of Formula II wherein R and R1 each represent a lower alkylgroup, R2 represents the dimethylene radical, Y and Z each representhydrogen and M represents an alkali metal cation.
 5. A process asdefined in claim 1, wherein said hydrocarbon solvent defined under (b)is selected from xylene, monochlorobenzene, dichlorobenzene,trichlorobenzene, tetrahydronaphthalene, hexane, heptane, octane,decane, perfluorohexane, perfluoroheptane, cyclohexane, cyclohexene,dichloromethane, chloroform, carbon tetrachloride, trichloroethylene,tribromoethylene, tetrachloroethylene, trichloroethane,tetrachloroethane, 1,1,2-trichloro-2,2,1-trifluoroethane,1,1,1,2-tetrachloro-2,2-difluoroethane, pentachlorofluoroethane,1-chloro-3-fluoropropane, and mixtures thereof.
 6. A process as definedin claim 1, wherein said hydrocarbon solvent defined under (b) is alower aliphatic chlorinated hydrocarbon.
 7. A process as defined inclaim 6, wherein said lower aliphatic chlorinated hydrocarbon istetrachloroethylene.
 8. A process as defined in claim 1 wherein thefiber material is synthetic polyamide fibre material.